EP0845302B1 - Verfahren zur Herstellung einer Kunststofffolie, die so hergestellte Kunststofffolie und Verglasung mittels dieser Kunststofffolie - Google Patents

Verfahren zur Herstellung einer Kunststofffolie, die so hergestellte Kunststofffolie und Verglasung mittels dieser Kunststofffolie Download PDF

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Publication number
EP0845302B1
EP0845302B1 EP97402703A EP97402703A EP0845302B1 EP 0845302 B1 EP0845302 B1 EP 0845302B1 EP 97402703 A EP97402703 A EP 97402703A EP 97402703 A EP97402703 A EP 97402703A EP 0845302 B1 EP0845302 B1 EP 0845302B1
Authority
EP
European Patent Office
Prior art keywords
sheet
lacquer
plastics material
varnish
hard
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97402703A
Other languages
English (en)
French (fr)
Other versions
EP0845302A1 (de
Inventor
Jean-Louis Bravet
Bernard Bureau
Claude Didelot
Claude Morin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP0845302A1 publication Critical patent/EP0845302A1/de
Application granted granted Critical
Publication of EP0845302B1 publication Critical patent/EP0845302B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets

Definitions

  • the present invention relates to the preparation of sheets of material plastic, in particular intended for applications in which a excellent transparency, or other optical properties, are required. This is the case, for example, with glazing in buildings or vehicles transport, which we could consider replacing, at least for meet special requirements with material sheets plastic.
  • Plastics are lighter compared to glass, which which is a decisive advantage for urban vehicles with electric motor, to the extent that an increase in their autonomy is crucial. In such vehicles, you could even consider making plastic doors in one block entire or even complete sides of the bodywork, including windows, and possibly paint a lower part.
  • the lightness of the transparent surfaces is interesting relative to modern transport vehicles, insofar as the technical progress goes hand in hand with integrating functions into glazing always more numerous (rear window heating, radio antenna, defrosting the windshield, coloring to prevent heating of the passenger compartment in strong sunshine, incorporation of compounds electrochromic, display of information on the windshield ...), and with ever increasing glass surfaces. This results in an increase general harmful vehicle in terms of energy consumption.
  • plastics are likely to provide, compared to glass, improved safety conditions, and a superior theft protection, due to their superior resilience.
  • the ability of the plastic sheets to be more or less reversibly deformed allows to consider modes installation in considerably simplified bodywork bays, snap-in, both inside and outside the vehicle.
  • strips are formed by extrusion plastic sheets, we cut a piece to the dimensions required, it is fixed on a thermoforming device, we proceed to thermoforming by contact with at least one solid mold surface and, possibly with compressed air or with suction. Properties optics of a sheet thus extruded are not satisfactory.
  • the injection of the plastic in a mold of suitable shape is proportional to that of the shapes that we want to obtain; the cost of these devices is affected.
  • this technique lacks flexibility, in the sense that each shape of part to obtaining it requires the use of a particular injection device. What is more, when non-substantially planar shapes, more than slightly domed, or complex in any other way, are targeted, an inhomogeneous distribution of the material is observed in the mold, even if the operating conditions are strictly observed optimal, such as temperature / viscosity, pressure. This inhomogeneity harms the optical properties of the product.
  • the shaping is carried out by contact with a solid surface, generally metallic.
  • a solid surface generally metallic.
  • the third step of the process which consists in heating said assembly, can be carried out according to two main variants.
  • At least one central part not coated with varnish of at least one side of the plastic sheet is in contact with a surface capable of guaranteeing the required optical properties of the final product, especially with a glass surface.
  • the third step is carried out with at minus a central part of the sheet coated with varnish free of all mechanical contact, i.e. only subject to the action of gravity.
  • the sheet prepared at the end of the first injection step is substantially flat or slightly curved. Indeed it is much more easy to obtain a perfectly polished mold surface for such simple shapes, especially since the surface of the sheet is important. Correlatively, obtaining transparent surfaces having good optical properties is then facilitated. Otherwise, initially injecting the sheet in a simple form, practically flat, guarantees a homogeneous distribution of the material in the mold, also favorable from the optical point of view.
  • the same injection mold can be used for the manufacture of right elements and left elements, in plane shapes in a first step, a possible subsequent bending operation which may be preceded, as the case may be, by a turning operation.
  • the plastic sheet at least partially coated with varnish is maintained during the step heating in the material softening area, on support peripheral and bulging, similarly to what is commonly used for glass.
  • the plastics which can be used to implement the invention are, for example, polycarbonate (PC) as obtained in particular from of Bisphenol A or similar aromatic molecules, the poly (methyl methacrylate) (PMMA), acrylic copolymers, ethylene copolymers such as ethylene / acrylic derivatives (EDA), thermoplastic polyesters such as poly (ethylene glycol terephthalate) (FART).
  • PC polycarbonate
  • PMMA poly (methyl methacrylate)
  • EDA ethylene copolymers
  • EDA ethylene copolymers
  • thermoplastic polyesters such as poly (ethylene glycol terephthalate) (FART).
  • the method of the invention comprises two embodiments distinct.
  • the varnish is applied to the sheet of material plastic in the form of a liquid precursor, then optionally dried by applying a moderate temperature and / or radiation, before being hardened in any case by heating to a temperature at least equal to the softening temperature of the plastic.
  • a moderate temperature and / or radiation for example, a heat source, a heat source, a heat source, or a heat source.
  • the varnish more or less liquid or viscous as it hardens, conforms to the shape of the leaf in the softened state, which changes if necessary gradually to its desired final form. Therefore, the implementing relatively high temperatures would result, besides completing chemical reactions such as condensation and polymerization of the varnish, somehow create, according to this first variant, a mechanical anchoring of the varnish on its substrate, while avoiding any cracking or chipping of this varnish.
  • the hard varnish then consists of networks of mineral and organic molecular chains intertwined and linked to each other by means of silicon-carbon bonds.
  • a varnish composite has excellent transparency, adhesion and scratch resistance. It seems that the mineral network gives the coating its hardness and scratch resistance, the organic network its elasticity and resilience.
  • Such varnishes are well known and have been described in published applications EP-A1-0 524 417 and EP-A1-0 718 348; some are especially designated by the registered mark "Ormocer” which is the abbreviation for "Organically modified ceramic".
  • the cooking temperature is easily adaptable by variation relative proportions between organic polymer fraction and fraction mineral.
  • the plastic we know some constituents likely to influence the temperatures of softening.
  • the aforementioned application EP-A1-0 718 348 describes copolycarbonates obtained from Bisphenol A and diphenols functionalized with cycloalkyl groups such as cyclohexyl: the larger the fraction thus functionalized, the higher the temperatures softening are high.
  • the liquid precursor of the varnish can be applied to the substrate by flow coating, soaked in particular in a small volume bath in economy, spraying liquid or curtain.
  • the precursor is consisting for example of colloidal dispersions in solvents of several hybrid compounds, that is to say both organic and mineral, or low molecular weight polymers functionalized with SiOR groups mixed with tetraethoxysilane.
  • the hardening varnish then takes place according to a sol-gel process, in which the precursor is first dried, passing through the intermediate state of a gel, by moderate radiation or heating, in particular in the latter case to less than 50 ° C; curing is completed by ultraviolet radiation, or heating to temperatures greater than or equal to 140 ° C, preferably at 170 ° C and particularly preferably at 180 ° C, and less than or equal to 240 ° C, preferably 230 ° C and so particularly preferred at 200 ° C.
  • the hard varnish is formed before the process step of heating in the field of softening of the plastic.
  • this training is carried out cold and / or according to plasma assisted deposition such as CVD (Chemical Vapor Deposition) plasma.
  • CVD Chemical Vapor Deposition
  • a subsequent bending of the sheet is carried out on peripheral support, the chemical composition of the varnish so that it can be bent. In these conditions, we avoid without difficulty any flaking problem.
  • the varnish used in this second embodiment is only mineral and consists in particular of polysiloxanes.
  • varnish having a hardness gradient more precisely an increasing hardness of the plastic sheet constituting the substrate to the outside.
  • This type of varnish was made by depositing successive layers of different compositions and / or by progressive variation of the composition a single layer of varnish during its deposition process.
  • an increase in hardness corresponds an increase in the proportion of mineral chains compared to that of organic chains.
  • the injection advantageously makes it possible to form periphery of the sheet a relief and / or extensions such as ribs, profiles, legs or ears, and / or to have within the plastic material one or more inserts, in particular metallic.
  • This layout is particularly useful for gripping or fixing the sheet during its subsequent processing operations, by example during the heating stage, as well as for the final assembly for which it is intended, as in a vehicle body bay automobile.
  • the formation of peripheral profiles adapted to consider mounting the sheet from the inside of the vehicle, that is to say by the passenger compartment.
  • the bead of glue is then placed under the edge of the body bay and is not exposed to rays solar. Protecting the bead of glue with a varnish formed by periphery of the inner side of the leaf naturally becomes superfluous.
  • the appendages formed at the periphery of the leaf during its injection can be kept, or sawn in whole or in part according to their use. Sanding can be provided after such sawing.
  • a peripheral profile of symmetrical geometry with respect to the plane of the sheet may be appropriate, for example in the case of surfaces side transparencies of transport vehicles, either part profile that can be sawn later, depending on whether it is the element transparent right or left.
  • any inserts may be linked to the incorporation in the sheet of particular functions, such as a stop light in a rear window.
  • the present invention also relates to a flat sheet or domed transparent plastic-based, preferably polycarbonate, provided on at least part of at least one of its sides, a coating of hard varnish made up of molecular chains mineral and organic intertwined and connected to each other by silicon-carbon bonds, the sheet having been submitted after application of the varnish, or at least a precursor thereof, to a temperature at least equal to the softening temperature of the plastic material, in the absence of any other mechanical contact from a central part to the less of the sheet than that with plastic of said sheet.
  • a flat sheet or domed transparent plastic-based, preferably polycarbonate provided on at least part of at least one of its sides, a coating of hard varnish made up of molecular chains mineral and organic intertwined and connected to each other by silicon-carbon bonds, the sheet having been submitted after application of the varnish, or at least a precursor thereof, to a temperature at least equal to the softening temperature of the plastic material, in the absence of any other mechanical contact from a central part to the less of the sheet
  • the thickness of the hard varnish coating is greater than 3 ⁇ m, preferably 5 ⁇ m while remaining less than 10 ⁇ m, preferably 8 ⁇ m.
  • the scope of the invention also extends to applying the sheet previously described as a part automobile comprising a transparent part forming glazing and as than automotive glass.
  • a varnish is applied according to the example of published application EP-A1-0 718 348, on a polycarbonate sheet prepared from Bisphenol A and not, in particular, from diphenols functionalized with cycloalkyl groups. It is a standard, unmodified polycarbonate, marketed by the Company BAYER AG under the registered trademark "Makrolon", and whose glass transition temperature T g is equal to 145 ° C. The sheet has the dimensions 105 x 150 x 3 mm. After drying, the varnish film, identical to that described in the previous application, is also 5 ⁇ m thick.
  • the varnish is cured at a temperature of 155 ° C for 30 min, the sheet being simultaneously held on peripheral support and deforming by bending.

Landscapes

  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Claims (18)

  1. Verfahren zur Herstellung einer in mindestens einem Teil wenigstens einer Seite mit einem ausgehärteten Lack beschichteten Kunststoffscheibe, das die Stufen umfasst, die aus:
    1) Herstellen einer Kunststoffscheibe durch Spritzgießen,
    2) Aufbringen des Lacks auf dieser Scheibe und
    3) Erwärmen des Ganzen auf eine Temperatur, die mindestens gleich der Erweichungstemperatur des die Scheibe bildenden Kunststoffs ist, wobei der Lack in wenigstens einem zentralen Teil des Ganzen keinen anderen mechanischen Kontakt als den mit dem Kunststoff der Scheibe hat,
    bestehen.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der dritten Stufe, die aus der Erwärmung des Ganzen besteht, wenigstens der nicht mit Lack beschichtete zentrale Teil mindestens einer Seite der Scheibe sich mit einer Fläche, insbesondere einer Glasfläche, in Kontakt befindet, die in der Lage ist, die optischen Eigenschaften zu gewährleisten, die vom Endprodukt verlangt werden.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der dritten Stufe, die aus der Erwärmung des Ganzen besteht, wenigstens der zentrale Teil davon von einem mechanischen Kontakt frei ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die in Stufe 1) hergestellte Scheibe im Wesentlichen plan oder leicht gebogen ist.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass in Stufe 3) die Kunststoffscheibe auf einer Umfangsauflage gehalten und einem Biegevorgang unterworfen wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Lack in Stufe 2) in Form eines flüssigen Vorläufers, der anschließend gegebenenfalls durch eine geeignete Temperatur oder Strahlung getrocknet und schließlich in Stufe 3) ausgehärtet wird, auf die Kunststoffscheibe aufgebracht wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Charakter von Lack und Kunststoff derart gewählt wird, dass die Aushärtungstemperaturen des ersten wenigstens teilweise mit den Erweichungstemperaturen des zweiten bei Werten von größer als oder gleich 140 °C, vorzugsweise 170 °C, und besonders bevorzugt 180 °C und kleiner als oder gleich 240 °C, vorzugsweise 230 °C, und besonders bevorzugt 200 °C übereinstimmen.
  8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Lack als Additive UV-Filter, Sonnenschutzmittel und/oder Farbpigmente enthält.
  9. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der ausgehärtete Lack aus Netzen aus anorganischen und organischen Molekülketten besteht, die einander durchdringen und durch Kohlenstoff-Silicium-Bindungen miteinander verknüpft sind.
  10. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der ausgehärtete Lack vor Stufe 3) gebildet wird.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass der ausgehärtete Lack in der Kälte und/oder durch eine plasmagestützte Beschichtung wie Plasma-CVD gebildet wird.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass der ausgehärtete Lack ausschließlich anorganisch ist und insbesondere aus Polysiloxanen besteht.
  13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass der Lack des fertigen Erzeugnisses einen nach außen zunehmenden Härtegradienten aufweist, der durch sukzessives Aufbringen von Schichten mit unterschiedlicher Zusammensetzung und/oder durch fortschreitende Veränderung der Zusammensetzung einer einzigen Lackschicht im Laufe ihres Beschichtungsverfahrens erhalten wird.
  14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass in der Stufe 1) zur Herstellung der Kunststoffscheibe durch Spritzgießen am Scheibenumfang Überdicken für eine mechanische Verstärkung und/oder ein Relief und/oder Verlängerungen wie Rippen, Profile, Laschen oder Ösen gebildet werden und/oder im Kunststoff eine oder mehrere insbesondere metallische Einlagen angeordnet werden.
  15. Scheibe, die transparent und plan oder gebogen ist, im Wesentlichen aus einem Kunststoff wie Polycarbonat besteht, der mit einer ausgehärteten Lackschicht beschichtet ist, die aus Netzen aus anorganischen und organischen Molekülketten gebildet ist, die einander durchdringen und durch Kohlenstoff-Silicium-Bindungen miteinander verknüpft sind, und nach Aufbringen des Lacks, gegebenenfalls in Form eines flüssigen Vorläufers, einer Erwärmung auf eine Temperatur, die mindestens gleich der Erweichungstemperatur des Kunststoffs ist, unterworfen worden ist, wobei kein weiterer mechanischer Kontakt des Lacks wenigstens eines zentralen Teils der Scheibe als derjenige mit dem Kunststoff dieser Scheibe besteht.
  16. Scheibe nach Anspruch 15, dadurch gekennzeichnet, dass die Dicke der ausgehärteten Lackschicht mehr als 3 µm und vorzugsweise 5 µm und weniger als 10 µm und vorzugsweise 8 µm beträgt.
  17. Verwendung einer Scheibe nach Anspruch 15 oder 16 als Autoteil, das einen transparenten Teil enthält, der eine Verglasung bildet.
  18. Verwendung einer Scheibe nach Anspruch 15 oder 16 als Autoglas.
EP97402703A 1996-11-26 1997-11-13 Verfahren zur Herstellung einer Kunststofffolie, die so hergestellte Kunststofffolie und Verglasung mittels dieser Kunststofffolie Expired - Lifetime EP0845302B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9614403 1996-11-26
FR9614403A FR2756292B1 (fr) 1996-11-26 1996-11-26 Procede de preparation d'une feuille en matiere plastique, cette feuille et vitrage la comportant

Publications (2)

Publication Number Publication Date
EP0845302A1 EP0845302A1 (de) 1998-06-03
EP0845302B1 true EP0845302B1 (de) 2002-07-24

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EP97402703A Expired - Lifetime EP0845302B1 (de) 1996-11-26 1997-11-13 Verfahren zur Herstellung einer Kunststofffolie, die so hergestellte Kunststofffolie und Verglasung mittels dieser Kunststofffolie

Country Status (9)

Country Link
US (1) US6054189A (de)
EP (1) EP0845302B1 (de)
JP (1) JP4251678B2 (de)
KR (1) KR100527856B1 (de)
BR (1) BR9705846A (de)
DE (1) DE69714195T2 (de)
FR (1) FR2756292B1 (de)
PL (1) PL190239B1 (de)
PT (1) PT845302E (de)

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US10597097B2 (en) 2015-09-07 2020-03-24 Sabic Global Technologies B.V. Aerodynamic features of plastic glazing of tailgates
WO2017042699A1 (en) 2015-09-07 2017-03-16 Sabic Global Technologies B.V. Molding of plastic glazing of tailgates
WO2017042698A1 (en) 2015-09-07 2017-03-16 Sabic Global Technologies B.V. Surfaces of plastic glazing of tailgates
KR20180082561A (ko) 2015-11-23 2018-07-18 사빅 글로벌 테크놀러지스 비.브이. 플라스틱 글레이징을 갖는 윈도우를 위한 라이팅 시스템
KR101938268B1 (ko) 2016-09-20 2019-04-11 (주)승보산업 플라스틱의 금속제 코팅을 위한 제조방법 및 이로부터 수득된 플라스틱 가공품
CN108239295A (zh) * 2016-12-26 2018-07-03 科思创聚合物（中国）有限公司 具有提高的铅笔硬度的聚碳酸酯复合物

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Also Published As

Publication number Publication date
BR9705846A (pt) 1999-05-18
FR2756292B1 (fr) 1998-12-24
JP4251678B2 (ja) 2009-04-08
FR2756292A1 (fr) 1998-05-29
JPH10180183A (ja) 1998-07-07
DE69714195T2 (de) 2003-02-27
KR19980042670A (ko) 1998-08-17
PT845302E (pt) 2002-11-29
EP0845302A1 (de) 1998-06-03
PL323338A1 (en) 1998-06-08
KR100527856B1 (ko) 2006-02-13
DE69714195D1 (de) 2002-08-29
US6054189A (en) 2000-04-25
PL190239B1 (pl) 2005-11-30
MX9708809A (es) 1998-08-30

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